Polymeric compositions from divinyl sulfone



Patented Apr. 25, 1950 Q j UNITED STATES. PATENT OFFICE" rotmmcoomggi ggrgilws monmvnwr.

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Serial No 87,5 1 6 Claims. '(OI. 260-79.!) f This invention relates to new polymers formed Ammo" I by the addition of polyhydric chemicals and specifically polyhydric alcohols or thiols, to sul- I 11,1 fone activated ethylenic linkages, and methods of OHs=onsoiH==om preparing same. Isopropenyl eulfone An object of the invention is the preparation v on, of new and useful polymer compositions. An- (CHFCLMM, other object is the preparation of polymers use- P 1 mm a ful as thermoplastic molding compositions. A further object is the formation of polymers which can be extruded as filaments for the production 2-bit (vinyl sulron l ethane of fibres. Other objects will be apparent from cm=cnso|cmcmsmcn=cr the following disclosure. 1,4bis (vinyl sultonyl) butane The polymers are-postulated as having he CHs=GH80|(OHa)80|GH=OHa condemn! unit l Bis (vinyl suifonyl) methane E n o H n (CHFCHBOPhCHa -x-ns-x-.d-dd-dywi B l ne I h is 1&1 lHi 1 I=CH;-):8Oa where x is a member from the-class consisting 2o Alpm'ethyl g of oxygen and sulfur; R1 and R: are from the class consisting of hydrogen. alkyl and aryl, at P n least oneof the R1 and R: groups being hydrogen; Alpha-n-propyl vinyl lulfone- R: is a divalent organic radical. on,

More particularly, the invention is concerned {J, with the formation of polymers from glycols and M n 1 vi 1 H n dithiols with compounds containing two vinyl p 5 roups (Jim B oHpd-hso, who) The donor compound'is a monomeric compound adjacent to a sulfone group whereby in the polyhaving two terminals HX-- groups, where X is mer the condensation unit preferably 0 or 8, each being directly attached to a acyclic hydrocarbon, or a benzene nucleus.

0 The acyclic hydrocarbon chain may be separated or not separated by intervening radicals such as amido, ester, oxygen, sulfur, as illustrated 1 frmed by the following: It is customary to speak of the molecule supplying the active hydrogen as the donor, and the, molecule containing the ethylenic linkage asthe Ethylene glycol acceptor. To assure theformation of polymeric 2:3'but51ene glycol materials substantially stoichiometric equivalents methylene of donor and acceptor should be used. The usual Tetmmethylene glycQl addition occurs with the hydrogen adding to the necamethylene glycol carbon alpha to the sulfone group, as shown in Hydroqumme the structural unit pictured first above. However, Resm'ciml a is possible that some of the hydrogen addition Catechol Bis-beta-hydroxyethyl adipamide 1 th t bo tom iving th takes p ace on e be a a g e Bis-beta-mercaptoethyl adipate ctural unit Sm y i Ethylene dithiol n i- Trimethylene dithiol g I Decamethylene dithiol I Bis-(b-thiol ethyl) ether R1 1 2-thiol ethanol I Thio-diglycol (HOCH2'CH2.):S

fonyl chemical having" from one to t inter, Bis-(beta hydroxyethyl) sulfone mediate sulfonyl radicals each linked to a ter- 1 The polymerization is conveniently carried out minal vinyl group or a substituted vinyl group by mixing a catalyst with the active hydrogen as illustrated by the following: compound (donor) and adding the unsaturated acoaeee monomer (acceptor). This should be done slowly as the reaction is frequently exothermic. At the end of the addition the mixture is heated to com-' plete the reaction. An inert solvent may be employed, if desired. Suitable inert solvents include water, dioxane, chloroform, benzene, toluene, diethyl ether and ethylene dichloride. Although .water will react with the vinyl sulfone it may be used as a solvent since its rate of reaction'is much slower than the glycols or dithiols.

As catalysts, we may employ any base or alkali which is unreactive with the sulfone, and which has a basic strength at least equivalent to sodium acetate such as tertiary amines having a dissociation constant in water of at least 1.8 10 at 25 C. as well as the quaternary ammonium hydroxides, the alkali and alkaline earth metals, their oxides, hydrides and carbonates, as illustrated by triethyl amine, tributyl amine, trimethyl benzyl ammonium hydroxide, tetramethyl ammonium hydroxide, potassium hydroxide, sodium hydroxide, sodium ethoxide, sodium hydride, phenyl lithium, potassium carbonate,

metallic sodium, barium, calcium, etc.

The amount of catalyst necessary, is small; satisfactory polymerizations being obtained with as little as one hundredth molar percent. In most cases the polymerization proceeds rapidly at room temperature and requires external cooling. Satisfactory polymerizations are obtained at temperatures varying from C. to about 200 'C. Still lower temperatures may be employed at a sacrifice in reaction times while higher temperatures are limited only by the stability of the reactants or their polymers.

The polymerization is usually allowed to proceed until it has substantially exhausted itself. Acids, in addition to'terminating the reaction, reduce the color of the final polymer.

Polymers produced by this process vary from Example 1 Vinyl sulfone (0.005 mole) is added to 0.005 mole of ethylene glycol in which a small piece of sodium has been dissolved. The mixture becomes yellow and considerable heat is developed. On cooling, the mass sets to a viscous jelly. Neutralization of the sodium with alcoholic hydrochloric acid, converts the product to a wax-like solid which melts around 60 C. The copolymer is only slightly soluble in acetone, dioxane and benzene, but can be recrystallized from water.

Example 2 A small piece of sodium is dissolved in 0.1 mole of trimethylene glycol and 20 ml. or dioxane is added. To this mixture is added a solution of 0.1.

mole vinyl sulfone in 20 ml. of dioxane at such a rate that the temperature does not exceed 70 C. After 5 hours at 55 C., the product crystallizes on cooling to 25 C. The copolymer may be isolated as a waxy, white solid by pouring the warm solution into volumes of cold methanol A mixture of 0.005 mole each of vinyl sulfon and trimethylefi'glycdl are poured into 5 ml. of

an aqueous 20% sodium hydroxide solution. The solution becomes warm and the copolymer precipitates as viscous oil.

Erample 4 A small piece of sodium is dissolved in 0.10 mole of trimethylene glycol, and 0.10 mole of vinyl sulfone is added slowly, keeping the temperature at about 100 C., at the end of addition the product is a thin oil. The mixture is then heated overnight at 170 C. which converts it to a viscous liquid. On cooling it solidifies to a hard brittle resin.

Example 5 A mixture of 0.01 mole each of vinyl sulfone and N,N'-di-(beta-hydroxyethyl)-adipamide is treated with 7 ml. of 20% sodium hydroxide. The

reaction mixture becomes warm and within 5 minutes a solid, white copolymer forms on the surface of the liquid.

Example 6 I dried at 65 C. It is a pure white powder which melts under slight pressure at C. but the melt does not fiow readily until the temperature reaches C. Even at this temperature the melt remains very viscous. On cooling, the melt sol difies to an opaque, white, porcelain-like solid.

Example 7 A mixture of 0.5 ml. each of vinyl sulfone and trimethylene dithiol is treated with one drop of tributyl amine. The mixture reaches the boiling point within 30 seconds and, on cooling, sets to a hard, opaque resin.

Example 8 A mixture of 6.90 g. of bis-(beta-mercaptoethyl) -ether and 5.90 g. of vinyl sulfone are added in 0.5 ml. portions to a test tube containing one drop of a concentrated solution of sodium methoxide in methanol. The reaction is very vigorous and the temperature exceeds 150 C. during the early part of the addition. After about half the mixture has been added, two more drops of catalyst solution are stirred into the reaction mixture and the addition is completed. At this point the copolymer is a low viscosity colorless liquid at 150 C. which solidifies on cooling to a waxy solid.-f1he tube is flushed with nitrogen and placed in a" C. metal bath overnight. This causes a marked increase in melt viscosity. On cooling the copolymer sclidifies very rapidly to a hard, opaque, off-white solid.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

1. A polymeric addition product of equimolecuiar proportions of a monomeric glycol from the class of dihydricglycols and dithioglycols, and a monomeric auitonyl chemical having from one to two intermediate sulionyl radicals each linked to a terminal, radical from the class consisting lar proportion: .02 a monomeric glycol from the 8 6 dihydriczlycols and dithiollycolr, and oulioae.

. DWIGHT 1-. 8080383.

REFERENCES CITED The following references are of record in the tile of this potent:

, UNITED STATES PATENTS e m o ammo Number Name Date 2,201,884 Carothers May 21, 1940 2,847,182 Coilman Apr. 25, 1944 2,348,705 Alderman May 16, 1944 OTHER-REFERENCES Btalimann: Jour, Organic Chemistry, vol. II, pares 719-785, November 1948. 

1. A POLYMERIC ADDITION PRODUCT OF EQUIMOLECULAR PROPORTIONS OF A MONOMERIC GLYCOL FROM THE CLASS OF DIHDRICGLYCOLS AND DITHIOGLYCOLS, AND A MONOMERIC SULFONYL CHEMICAL HAVING FROM ONE TO TWO INTERMEDIATE SULFONYL RADICALS EACH LINKED TO A TERMINAL RADICAL FROM THE CLASS CONSISTING OF VINYL AND MONOHYDROCARBON-SUBSTITUTED VINYL. 